4, 4&#39;-bis [(4-nu-2-sulfoethylamino)-6-sulfophenoxy-s-triazin-2-ylamino]-2, 2&#39;-stilbenedisulfonic acid brighteners



I ing to the following general formula: a Slush of gr United States Patent 0 ce 3,350,395

Patented Oct. 31, 1967 Th t a t i 3,350,395 e brigh eners charac erized by the foregoing general formula are prepared by condensing, in the conventional manner, approximately one mole of 4,4'-diaminostilbene R BENEDISULFONIC ACID BRIGHTENE s di sulfonicacid with approximately 2 moles of cyanuric Albert R strobe], Delmar and Sigmund C ti 5 'ClIlOI'ldfi and this product in turn condensed with 2 moles Ca fl mn, NY, assignors to General A ili & of a phenolsulfonic acid (either a monoor di-sulfonic Film Corporation, New York, N. a corporation acid) and then with 2 moles of either taurine, N-methyL of Delaware taurine or N-ethyltaurine. If desired, an excess of up to N0 Drawmg- F 21, 1966, 588,325 about of' any of the reactants may be employed 3 Chums (CL 260 240) 10 While this order of condensation is preferred it can be varied. For example, the cyanuricchloride can be condensed with the phenolsulfonic acid, then with taurine, N- ABSTRACT OF THE DISCLOSURE methylt'aurine or N-ethyltaurine and finally with 4,4'- di- A new class of brightener compounds of the stilbenei tilb di ulfo ic id cyanuric type having a total number of eight sulfonic acid Th phenolsul-fonic a id which may be employed have groups and having, solubility in acidic medium of a pH the formula: of about 1 are obtained by first condensing one mole of OH 4,4-diaminostilbene disulfonic. acid with approximately I 2 moles of cyanuric chloride and condensing the resulting product with 2' moles of a phenoldisulfoni'c acid and then X 11, with 2 moles of either taurine, N-methyltaurine or N- ethyltaurine. I

wherein" rt and X have the same values as above and are exemplified by o-phenolsulfonic acid m-phenolsulfonic acid p-phenolsulfonic acid 6-methyl-phenol-3-sulfonic acid 6-methyl-phenolA-sulfonic acid phenol-2,4-disulfonic acid phenol-2,5-disulfonic acid This application is a continuation-in-part of our application Ser. No. 272,534, filed on- April 12', 1963-; now abandoned.

This invention relates to a novel class of brightener compounds of the stilbene-cyanuric type having solubility in acidic medium of a pH of about 1.

The art is replete with. various brighteners of the stilbene-cyanuric acid chloride type. Such brighteners, howphenoblidl-sulfom-c acid are not m a H of abollt 4-m'ethyl-phenol-2,6-disulfonic acid 1, 1.e., they readily precipitate in dilute mineral ac1d medium, and as a consequence cannot be employed as The following examples will illustrate the invention,

brightening agents with atio i finishing agents on celbut are not intended to be limitative thereto. Unl'e'ss otherlulo i media, Wise specified, the parts. are by We1ght.- Accordingly, the principal object of the present fIl-Vfil'lr EXAMPLE I tion is to provide. a new class of brightener compounds of the stilbene-cyanuric type having solubility in acidic l N 0 medium, i.e., acid' soluble at a pH of about 1, and par- H- TSOaNa cationic surface active agents (cationic synthetic detersoaNa KC) gents) on cellulosic media, with alum and rosin size 1n I paper making, with casein-clay coatings on. paper, and 5 other uses on cellulosic materials yielding brighter CECHZSOBNZ, 2

hues Sodium 4,4 'bis[4-(N Inethyl-N-2-sulfoethylamin0)-6-p-sulf0- Other ObJBCilS and advantages Wlll appear hereinafter. phenoxy-s-triazur-Z-ylamino]-2,2-stilbenedisulfonate The above objects are accomplished by utilizing a 15 grams of cyanurie chloride were dissolved in 65 cc. brightening agent characterized by a structure correspondof acetone at 30 C. This was downed under agitation in ams of ice chips and 20 cc. of water.

N 30 M), At a temperature of 8-' to 2"" there were gradually added 148- cc. of a 10% by weight per volume of an 1, M aqueous solution of 4,4'-diamino-2 ,2 stilbenedisulfonic 03M N acid (0.04 mole) while maintaining the pH neutral Y (Congo delta) with 25 ml. of 20% aqueous soda ash N I solution The mixture was stirred for 1 hour at about 0 \GHZCHIS'OSM 27 C to a negative amlne test. There were then added 18 8 V p v grams of sodium p-pherrolsulfonate. 2H O' (0:08 mole). WhefelnM represents either hydrogen alkali s. The material was stirred 5 hours at 35 C., keeping the Le, lithium, sodium or potassium, n represents a posipH faintly phenolphthalein alkaline by addition of 16 cc. tive integer of from 1' to 2', and X and Y each represent of 20% by weight per volume of an aqueouscaustic soda either hydrogen, a methyl or ethylgroup.. solution. There were then added 38.6 grams of 31.7%

aqueous methyltaurine solution (0.088 mole). The material was stirred 3 hours at 65 C., then 6 hours at 95 C., the pH being maintained strongly phenolphthalein alkaline by the addition of 16 mls. of 20% aqueous caustic soda solution. It was finally treated with Nuchar (activated carbon), filtered and evaporated to dryness.

Application of brightener compound to cotton A piece of cotton cloth weighting approximately 100 grams was padded in the usual fashion with an aqueous suspension containing 1.43 grams of a cationic synthetic softening agent (commercially available under the brandname of Soramine CS) and 0.07 gram of the above brightener compound dissolved in 100 ml. of water. The padded cotton cloth was then squeezed out on rubber rollers and dried. This represents 1% detergent-.05% brightener dyeings. The treated cotton cloth has a very much brighter hue than a similar piece of cotton padded with an aqueous solution containing only 1.43 grams of the cationic synthetic softening agent.

Application of brightener compound in coating of alum sized bond paper Blank control 1 Brightener compound 32 Coatings on the same alum sized bond paper with an aqueous solution of the same concentration and pH were made with the following brightener compounds and comparative brightness readings determined:

Brightness reading at was L -NHCH2 (2 sulfonic acid groups) Q :02. NH-

L -NCH1CH1SO H (4 sulfonic acid groups) (3) r -NHCuH :ou NH -N(C2H OH):

SOsH 2 11 5 (2 sulfonic acid groups) .cn- -NH NHCflH5 (4 sulfonic acid groups) (6 suiionlc acid groups) From the foregoing results, it was surprising and unexpected that the brightness of the brightener compound of Example 1 increases substantially as the total number of sulfonic acid groups in such brightener compounds increases from 4 to 6, especially when the sulfoanilino in the triazin moieties are replaced by sulfophenoxy.

EXAMPLE II SOzNB l :on -NH(3 :-o soiNa N N SOaNB CH2CH2SOaNa 2 sodium 4,4-bis 6- (2,4-disulfophenoxy) -4- (N-methyl-N-2-sulfoethylamino) -S-triazin-2-ylamino] -2,2-stilbenedisulfonate Example I was repeated with the exception that 0.08 mole of sodium-p-phenolsulfonate was replaced by 23.8 grams (0.08 mole) of di-sodium phenol-2,4-dissulfonate.

The purified brightener compound, containing a total of 8 sulfonic acid groups, when coated on alum sized bond paper at the same concentration and pH as in Example I, gave a brightness reading at the peak of 38.

EXAMPLE III SOaNa CHnCHzSOsNB 2 Example I was repeated with the exception that methyl taurine was replaced by 11 grams (0.088 mole) of taurine,

giving a product having properties similar to that of the brightener of Example I in all application tests.

EXAMPLE IV S OaNa :CH C NH-l -0-9011,

so N 0 N a a T/CHB S a a N CHaCHzS OaNa 2 Example II was repeated with the exception that the di-sodium phenol-2,4-disulfonate was replaced by 25 grams (0.08 mole) of the di-sodium salt of 4-methylphenol-2,64lisulfonic acid, giving a product having properties similar to that of the brightener compounds of Example II in the application to alum sized bond paper.

From the foregoing illustrative examples it becomes clearly manifest that the brightener compounds of the present invention having from 6 to 8 sulfonic acid groups, are far superior to any previously known compounds containing from 2 to as high as 4 sulfonic acid groups when applied in a strong acid medium, i.e., at a pH. of about i.

3,350,395 6 We claim: 3. A brightener compound having the following for- 1. A brightener compound having the following formula: mula:

I" %N\ (S a )2 r N LlgoaNa :CH- NH-C C-O 1 ll =o1r NH-G CO-CH3 SOsM \C/Y X I 1 l I I SOaNa sO Na Il/ omomsom 2 wherein M represents a member selected from the class CHZCHZSOiNa 2 consisting of hydrogen and an alkali metal, and X and Y represent a member selected from the class consisting of hydrogen, methyl and ethyl groups. References (med 2. A brightener compound having the following for- UNITED STATES PATENTS mum: 2,846,397 8/1958 Ackermann 260-240 XR I N $103M 2,945,762 7/1960 Carroll et a1. 260240 XR :CH N114 -o- SO Na FOREIGN PATENTS N N 841,189 7/1960 Great Britain. some 43,527 9/1960 Poland.

1/ JOHN D. RANDOLPH, Primary Examiner.

CHaCHzSOgNB 2 

1. A BRIGHTENER COMPOUND HAVING THE FOLLOWING FORMULA: 